EP0096439B1 - Stabilisierungsmittel für Emulsionen - Google Patents

Stabilisierungsmittel für Emulsionen Download PDF

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Publication number
EP0096439B1
EP0096439B1 EP83200770A EP83200770A EP0096439B1 EP 0096439 B1 EP0096439 B1 EP 0096439B1 EP 83200770 A EP83200770 A EP 83200770A EP 83200770 A EP83200770 A EP 83200770A EP 0096439 B1 EP0096439 B1 EP 0096439B1
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EP
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Prior art keywords
process according
amadori rearrangement
rearrangement product
mixture
phosphatides
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Expired
Application number
EP83200770A
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English (en)
French (fr)
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EP0096439A3 (en
EP0096439A2 (de
Inventor
Klaus Hinrich Todt
Wilhelmus Adrianus Maria Castenmiller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to AT83200770T priority Critical patent/ATE24182T1/de
Publication of EP0096439A2 publication Critical patent/EP0096439A2/de
Publication of EP0096439A3 publication Critical patent/EP0096439A3/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H11/00—Compounds containing saccharide radicals esterified by inorganic acids; Metal salts thereof
    • C07H11/04—Phosphates; Phosphites; Polyphosphates
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/01—Other fatty acid esters, e.g. phosphatides
    • A23D7/013—Spread compositions
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23J—PROTEIN COMPOSITIONS FOR FOODSTUFFS; WORKING-UP PROTEINS FOR FOODSTUFFS; PHOSPHATIDE COMPOSITIONS FOR FOODSTUFFS
    • A23J7/00—Phosphatide compositions for foodstuffs, e.g. lecithin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the present invention relates to new Amadori rearrangement products, to a process for producing said products and to their use as stabilizing agents, particularly anti-spattering agents for edible water- and oil-containing emulsions, particularly W/O emulsions of the margarine-type.
  • margarines In the initial stage of the frying process, margarines separate essentially into an aqueous phase and an oil phase. When the temperature is increased above the boiling point of water, spattering occurs since the water evaporates vigorously entraining some of the oil phase.
  • Phosphatides such as mixtures of phosphatidyl choline, phosphatidyl-ethanolamine, phosphatidylinositol, originating from egg-yolk, soyabeans, rapeseed and maize have been used as emulsifiers and anti-spattering agents in margaines.
  • phosphatides are less active in the absence of sodium chloride or in the presence of very low levels (e.g. 0.4% or less) of sodium chloride.
  • Attempts have been made by the Applicants to improve the anti-spattering activty of phosphatides; these attempts resulted in the development of expensive purification methods and in the development of lysophosphatides i.e. partially hydrolyzed phosphatides. These partially hydrolyzed phosphatides are very effective anti-spattering agents but sometimes develop a bitter off-flavour.
  • the new products according to the invention are represented in Fig. 1, wherein R, and R 2 are identical or different, saturated or unsaturated fatty acid residues and R-CH 2 is a reducing carbohydrate selected from glucose, fructose, lactose and an oligosaccharide obtained by hydrolysis of starch.
  • R, and R 2 are preferably fatty acid residues generally occurring in the phosphatidyl-ethanolamine (PE) molecules as found in nature, which comprise fatty acid residues having 16-26 C-atoms, predominantly consisting of linoleic acid-, oleic acid- and palmitic acid-residues.
  • PE phosphatidyl-ethanolamine
  • the sugar moiety stems from lactose.
  • the structure of the preferred product according to the invention, which is derived from PE and lactose, is illustrated in Fig. 2.
  • the new Amadori rearrangement products according to the invention are produced according to a process comprising allowing phosphatidyl-ethanolamine or a mixture of phosphatides which contains phosphatidyl-ethanolamine, to react with a carbohydrate carrying a carbonyl group, i.e. a source of a reducing sugar, at a temperature ranging from 70 to 135°C under substantially moisture-free conditions.
  • reaction is therefore preferably carried out at a temperature ranging from 80 to 115°C.
  • the reaction is preferably carried out under moisture-free conditions, i.e. in a medium containing less than 5% water and preferably less than 2% water for a period which may vary from a few minutes to a few hours, e.g. 1-3 hours, preferably in the absence of a solvent.
  • a medium containing less than 5% water and preferably less than 2% water for a period which may vary from a few minutes to a few hours, e.g. 1-3 hours, preferably in the absence of a solvent.
  • solvents such as dimethylsulfoxide and chloroform, or triethylamine and dimethylformamide
  • the preferred starting material for the reaction is therefore produced by spray-drying in warm air a mixture of said phosphatides with e.g. milk solids.
  • the reducing sugar preferably consists of lactose, but may comprise mixtures of lactose and another reducing sugar such as glucose or fructose.
  • a suitable source for the reducing sugar may consist of milk solids such as skimmilk powder and whey powder, preferably in the form of a finely divided powder such as a spray-dried powder.
  • a preferred reaction mixture consists of a spray-dried mixture containing 35-55 wt.% phosphatides and 45 to 65 wt.% milk solids.
  • a crude or a purified mixture of phosphatides from soyabeans is preferably used, because it is readily available and relatively cheap.
  • Soyabeans contain considerable proportions of phosphatides (phosphatidyl-chlorine, phosphatidyl-ethanol-amine and phosphatidylinositol being the most important), which are separated from the oil after the extraction of oil with a solvent.
  • phosphatides phosphatidyl-chlorine, phosphatidyl-ethanol-amine and phosphatidylinositol being the most important
  • US-A-3 004 922 relates to a process for the preparation of stable emulsions of phosphatides comprising stirring a phosphatide containing naturally associated fat into an aqueous solution at 70-80°C containing a carbohydrate.
  • the aqueous alcohol employed in the process preferably contains no more than 25% alcohol.
  • GB-A-815 246 relates to a process for the preparation of a complex compound of a glycerine-difatty acid phosphoric acid amino-alcohol ester with a sugar, comprising allowing the ester to act on a hot solution of sugar in an aqueous ethyl alcohol with stirring. In the presence of substantial amounts of water, Amadori rearrangement products as defined in the present invention are not formed.
  • edible water- and oil-containing emulsions particularly W/O emulsion-spreads of the margarine type having good frying properties and a reduced tendency to spattering are provided which contain the new Amadori rearrangement products according to the invention.
  • Such emulsions can be produced by dispersing the Amadori rearrangement products either in the aqueous or in the fatty phase in a proportion preferably ranging from 0.05-5 wt.%, based on the total composition.
  • the above emulsion can also be produced by incorporating in either the aqueous phase or the fatty phase an effective proportion of a product obtained by reacting a mixture of phosphatides containing phosphatidyl-ethanolamine with a reducing-sugar-containing material as hereinbefore described.
  • a spray-dried mixture consisting of 45 wt. % of a mixture of soyaphosphatides and 55 wt. % milk solids was heated for about 1 1/2 hours at about 100°C in the absence of solvent..
  • the milk solids contained about 45% lactose and about 9% casein.
  • the reaction was considered as completed when analysis of the reaction product by thin layer chromatography, using Kieselgel-Fertig- platten (Merck) and a mixture of CHCI 3 :acetone:CH 3 0H:acetic acid:water in the following ratio: 10:4:2:2:1, demonstrated that the spot corresponding to phosphatidylethanolamine had disappeared and that a new spot corresponding to that of the Amadori product according to Fig. 2 appeared, below the spots corresponding to phosphatidyl-chloline and phosphatidyl-ethanolmaine.
  • the new spot gave a positive colour reaction with the Zinzadze reagent for P, a negative reaction for primary amino groups, a positive reaction to sugars (anisaidehyde/H 2 SO I ) and showed strong reducing properties typical for Amadori rearrangement compounds with alkaline o-dinitrobenzene, alkaline triphenyltetrazolium chloride, AgN0 3 .
  • the product could not be hydrolyzed in 0.1 N HCI and on cleavage with HJ0 4 the phosphatidyl- ethanolamine spot was regenerated.
  • saltless (sodium chloride-free) margarine comprising 84% fat and 16% of an aqueous phase, by dispersing it in the fatty phase.
  • the margarine obtained was used for shallow frying in a pan and the spattering behaviour was tested.
  • the frying test is carried out for about 8 minutes.
  • the anti-spattering properties of the saltless margarine containing the Amadori rearrangement product according to the invention were superior to those displayed by the saltless margarines containing mixture (a) or (b) and were comparable to those achieved by using mixture (c) ' .
  • the margarine containing the Amadori rearrangement product according to the invention had excellent organoleptic properties and no bitter taste could be perceived, whereas the margarine containing mixture (c) had a somewhat bitter taste.
  • the stability of the O/W emulsion containing the Amadori rearrangement product according to the invention was found to be superior.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Food Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Edible Oils And Fats (AREA)
  • Saccharide Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (19)

1. Amadori-Umlagerungsprodukt der Formel:
Figure imgb0004
worin R, und R2 identische oder verschiedene gesättigte oder ungesättigte Fettsäureeste sind und R-CH2 ein reduzierendes Kohlenhydrat, ausgewählt unter Glucose, Fructose, Lactose oder einem durch Hydrolyse von Stärke erhaltenen Oligosaccharid, ist.
2. Amadori-Umlagerungsprodukt nach Anspruch 1, dadurch gekennzeichnet, daß R, und R2 Fettsäurereste mit 16 bis 26 Kohlenstoffatomen sind, die vorwiegend aus Linolsäure, Ölsäure- und Palmitinsäureresten bestehen.
3. Amadori-Umlagerungsprodukt nach Anspruch 2, dadurch gekennzeichnet, daß das reduzierende Kohlenhydrat aus Lactose besteht.
4. Amadori-Umlagerungsprodukt nach Anspruch 1, dadurch gekennzeichnet, daß es von natürlichem Phosphatidylethanolamin und Lactose abgeleitet ist.
5. Verfahren zur Herstellung eines Amadori-Umlagerungsproduktes nach Anspruch 1, wobei Phosphatidylethanolamin oder eine Mischung von Phosphatidylethanolamin enthaltenden Phosphatiden bei einer Temperatur in dem Bereich von 70 bis 135°C unter im wesentlichen feuchtigkeitsfreien Bedingungen mit einem reduzierenden Kohlenhydrat umgesetzt wird.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Reaktion bei einer Temperatur in dem Bereich von 80 bis 115°C durchgeführt wird.
7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Reaktion in Abwesenheit eines Lösungsmittels durchgeführt wird.
8. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das reduzierdene Kohlenhydrat Lactose, Glucose, Fructose und/oder ein durch Hydrolyse von Stärke erhaltenes Oligosaccharid enthält.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß das reduzierende Kohlenhydrat aus Milchfeststoffen besteht.
10. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß die Milchfeststoffe aus Molkenpulver bestehen.
11. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß eine Mischung von Phosphatidylethanolamin enthaltenden Phosphatiden und Milchfeststoffen sprühgetrocknet und des witeren bei einer Temperatur in dem Bereich von 70 bis 135°C reagieren gelassen wird.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die sprühgetrocknete Mischung 35 bis 55 Gew.-% Phosphatide und 45 bis 65 Gew.-% Milchfeststoffe enthält.
13. Verfahren nach Anspruch 11 oder 12, dadurch gekennzeichnet, daß eine Mischung von Sojaphosphatiden verwendet wird.
14. Verfahren zur Herstellung einer stabilisierten wasser- und ölhaltigen Emulsion, wobei 0,05-5 Gew.-% des in irgendeinem der vorhergehenden Ansprüche 1 bis 4 beanspruchten oder nach irgendeinem der vorhergehenden Ansprüche 5 bis 13 erhaltenen Amadori-Umlagerungsproduktes entweder in der wässrigen oder der Fettphase dispergiert oder gelöst werden.
15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, daß die Emulsion ein Wasser-in-Öl-Emulsionsaufstrich des Margarine-Typs ist.
16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, daß der Wasser-in-Öl-Emulsionsaufstrich des Margarine-Typs 0 bis 0,4% Natriumchlorid enthält.
17. Wasser- und ölhaltige Emulsion mit dem Gehalt von 0,05-5 Gew.-% eines Amadori-Umlagerungsproduktes, wie es in irgendeinem der Ansprüche 1 bis 5 beanspricht wird oder nach irgendeinem der Ansprüche 6 bis 14 erhaltlich ist.
18. Wasser-in-Öl-Emulsionsaufstrich, insbesondere eine Margarine nach Anspruch 17, die 0,05 bis 5 Gew.-% eines Amadori-Umlagerungsproduktes enthält, wie es in irgendeinem der Ansprüche 1 bis 5 beansprucht wird oder nach irgendeinem der Ansprüche 6 bis 14 erhältlich ist.
19. Margarine nach Anspruch 18 mit einem Gehalt an 0 bis 0,4% Natriumchlorid.
EP83200770A 1982-06-08 1983-05-31 Stabilisierungsmittel für Emulsionen Expired EP0096439B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83200770T ATE24182T1 (de) 1982-06-08 1983-05-31 Stabilisierungsmittel fuer emulsionen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8216630 1982-06-08
GB8216630 1982-06-08

Publications (3)

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EP0096439A2 EP0096439A2 (de) 1983-12-21
EP0096439A3 EP0096439A3 (en) 1984-05-30
EP0096439B1 true EP0096439B1 (de) 1986-12-10

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US (1) US4547387A (de)
EP (1) EP0096439B1 (de)
JP (1) JPS591499A (de)
AT (1) ATE24182T1 (de)
AU (1) AU547203B2 (de)
DE (1) DE3368267D1 (de)
ZA (1) ZA834124B (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5733933A (en) * 1984-03-19 1998-03-31 The Picower Institute For Medical Research Methods and materials for the diagnosis and treatment of conditions such as stroke
US5700447A (en) * 1992-05-21 1997-12-23 The Picowder Institute For Medical Research Methods and materials for the diagnosis and treatment of conditions such as stroke
US5801200A (en) * 1984-03-19 1998-09-01 The Picower Institute For Medical Research Methods and materials for the diagnosis and treatment of conditions such as stroke
US5733524A (en) * 1984-03-19 1998-03-31 The Picower Institute For Medical Research Methods and materials for the diagnosis and treatment of conditions such as stroke
US5869534A (en) * 1992-05-21 1999-02-09 The Picower Institute For Medical Research Glycosylation of lipids and lipid-containing particles, and diagnostic and therapeutic methods and materials derived therefrom
JP2501817B2 (ja) * 1987-03-27 1996-05-29 旭電化工業株式会社 乳化油脂組成物の製造法
JPH074162B2 (ja) * 1987-05-11 1995-01-25 日本油脂株式会社 離型油
US5008037A (en) * 1988-04-04 1991-04-16 Emulsion Technology, Inc. Emulsifier for water-in-oil emulsions
UA73327C2 (en) * 1999-11-15 2005-07-15 Water and oil emulsion

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB417552A (en) * 1933-12-18 1934-10-08 Metallgesellschaft Ag Process for the production of stable mixtures containing vegetable lecithin with or without soya oil
US2629662A (en) * 1948-06-17 1953-02-24 Glidden Co Process of treating phosphatides and product
GB815246A (en) * 1955-07-12 1959-06-24 Carl Heinz Buer Process for the preparation of new complex compounds of glycerine-di-fatty acid-phosphoric acid amino-alcohol esters with sugars
US3004922A (en) * 1955-12-17 1961-10-17 Buer Carl Heinz Emulsions of phosphatides in aqueous alcohol and their preparation
DE1302602C2 (de) * 1959-08-21 1973-09-20 N.V. Koninklije Stearine Kaarsenfabrieken, Gouda (Niederlande) Verfahren zur herstellung von beim ausbraten wenig oder nicht spritzender margarine
DE1900959A1 (de) * 1969-01-09 1970-08-27 Unilever Nv Verfahren zur Herstellung von Pflanzenphosphatiden mit universeller Emulgierkraft
US3690894A (en) * 1969-11-03 1972-09-12 Gerber Prod Process for preparing a dried rice cereal product
US3663235A (en) * 1970-04-13 1972-05-16 Lever Brothers Ltd Process of preparing margarine containing diacyglycerophatide
DE2345060C3 (de) * 1973-09-06 1982-04-22 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V., 3400 Göttingen 1,2-Dialkylketonglycerin-3-phosphatide und Verfahren zu deren Herstellung
US4399224A (en) * 1981-07-13 1983-08-16 A. E. Staley Manufacturing Company Enzymatically treated phosphatides
US4425334A (en) * 1982-04-02 1984-01-10 The Regents Of The University Of California Functional oxygen transport system

Also Published As

Publication number Publication date
JPS591499A (ja) 1984-01-06
ZA834124B (en) 1985-01-30
AU1537083A (en) 1983-12-15
EP0096439A3 (en) 1984-05-30
US4547387A (en) 1985-10-15
AU547203B2 (en) 1985-10-10
DE3368267D1 (en) 1987-01-22
EP0096439A2 (de) 1983-12-21
ATE24182T1 (de) 1986-12-15

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